N-2-hydroxy alkyl morpholine oxides

ABSTRACT

HYDROXY HIGHER ALKYL MORPHOLINE OIDES, AND FORMULATIONS CONTAINING THE SAME. THE COMPOUNDS HAVE MANY BENEFICIAL EFFECTS IN DETERGENT AND COSMETIC COMPOSITIONS. PARTICULARLY DESIRABLE FOR APPLICATION TO THE SKIN AND FOR MODIFICATION OF FOAMING POWER OF DETERGENT COMPOSITIONS.

United States Patent 3,637,682 N-Z-HYDROXY ALKYL MORPHOLINE OXIDES JohnFred Gerecht, Somerville, Null, assignor to Colgate- Palmolive Company,New York, N.Y. No Drawing. Filed Oct. 24, 1967, Ser. No. 677,723 lint.Cl. (107d 87/32 U.S. Cl. 260-2475 A 2 Ciaims ABSTRACT OF THE DISCLOSUREHydroxy higher alkyl morpholine oxides, and formulations containing thesame. The compounds have many beneficial effects in detergent andcosmetic compositions, particularly desirable for application to theskin and for modification of foaming power of detergent compositions.

This invention relates to morpholine oxides. One aspect of this relatesto morpholine oxides of the formula where R is a long chain alkyl groupof at least six carbon atoms, e.g. 6 to 20, preferably 10 to 14, carbonatoms.

It has been found that the compounds of this invention have beneficialand unusual characteristics, particularly suitable, for example, incosmetic and detergent applications.

The compounds described above may be prepared by reacting a long chain1,2 epoxide with morpholine, followed by the conversion of the resultingN-Z-hydroxyalkyl-morpholine to the corresponding N-oxide by oxidation,as with hydrogen peroxide.

Examples of Z-hydroxyalkyl groups are 2-hydroxydodecyl,2-hydroxyoctadecyl, 2-hydroxynonyl, Z-hydroxydecyl, 2-hydroxyundecyl,2-hydroxytridecyl, Z-hydroxytetradecyl, 2-hydroxypentadecyl,Z-hydroxyhexadecyl, and Z-hydroxyheptadecyl. Mixtures of compounds ofdifferent 2-hydroxyalkyl groups may be employed (e.g. a mixture in whichthese groups have 12-16 carbon atoms).

The compounds of this invention have many desirable attributes ofparticular value in emulsification and cleansing and detergency. Amongthese attributes are a desirable effect on the skin, and particularly anon-irritating and even anti-irritating effect when used in conjunctionwith surface active agents that ordinarily irritate the skin. The use ofthe compositions of the invention gives desirable modifications of thefoaming power and/ or foam characteristics of detergent compositions,such as a foam boosting effect. By using the new compounds valuablecompositions intended for application to the skin or hair (or for use incontact with the skin) may be formulated. This invention also providesnovel compounds of good miscibility with water which may be formulatedinto aqueous compositions which remain clear over a wide temperaturerange.

The novel compounds may be employed in detergent compositions, includinglight-duty liquids, heavy duty highly-built liquids, and granularcompositions in which they may, for example, be post-added tospray-dried built detergent powders. In such detergent compositions theymay be mixed with polymeric materials including agents for preventingredeposition of soil, such as sodium carboxymethylcellulose or polyvinylalcohol; opacifiers; perfumes; anti-tarnishing agents; bacteriostaticagents; and oxygenand chlorine-releasing bleaches. The novel compoundsmay also be used in hair-shampooing, hair-dyeing, or other hair-treatingor hair-conditioning compositions. The novel compounds may beincorporated in a variety of cosmetic compositions, including suchcompositions intended for application to the skin as skin lotions,creams, gels, or clear liquids.

In the use of the novel hydroxyalkyl morpholine oxides of this inventionin detergent compositions, the new compound may be used alone or may beadded to any of the conventional surface-active detergents. These may beof the anionic, non-ionic, cationic or amphoteric types, or mixturesthereof.

The anionic surface active agents include those surface active ordetergent compounds which contain an organic hydrophobic group and ananionic solubilizing group. Typical examples of anionic solubilizinggroups are sulfonate, sulfate, carboxylate, phosphonate and phosphate.Examples of suitable anionic detergents which fall within the scope ofthe invention include the soaps, such as the water-soluble salts ofhigher fatty acids or rosin acids, such as may be derived from fats,oils and waxes of animals, vegetable or marine origin, e.g., the sodiumsoaps of tallow, grease, coconut oil, tall oil and mixtures thereof; andthe sul-fated and sulfonated synthetic detergents, particularly thosehaving about 8 to 26, and preferably about 12 to 22, carbon atoms to themolecule.

As examples of suitable synthetic anionic detergents there may be citedthe higher alkyl mononuclear aromatic sulfonates such as the higheralkyl benzene sulfonates containing from 10 to 16 carbon atoms in thealkyl group in a straight or branched chain, e.g., the sodium salts ofhigher alkyl benzene sulfonates or of the higher alkyl toluene, xyleneand phenol sulfonates; alkyl naphthalene sulfonate, ammonium diamylnaphthalenesulfonate, and sodium dinonyl naphthalene sulfonate. In onepreferred type of composition there is used a linear alkyl benzenesulfonate having a high content of 3- (or higher) phenyl isomers and acorrespondingly low content (well below 50) of 2- (or lower) phenylisomers; in other terminology, the benzene ring is preferably attachedin large part at the 3 or higher (e.g. 4, 5, 6 or 7) position of thealkyl group and the content of isomers in which the benzene ring isattached at the 2 or 1 position is correspondingly low. Particularlypreferred materials are set forth in U.S. Pat. 3,320174, May 16, 1967,of J. Rubinfeld.

Other anionic detergents are the olefin sulfonates, including long chainalkene sulfonates, long chain hydroxyalkane sulfonates or mixtures ofalkenesulfonates and hydroxyalkanesulfonates. These olefin sulfonatedetergents may be prepared, in known manner, by the reaction of S0 withlong chain olefins (of 8-25, preferably 12-21 carbon atoms) of theformula RCH=CH R where R is 7 alkyl and R is alkyl or hydrogen, toproduce a mixture of sultones and alkenesulfonic acids, which mixture isthen treated to convert the sultones to sulfonates. Examples of othersulfate or sulfonate detergents are paraflin sulfonates, such as thereaction products of alpha olefins and bisulfites (e.g. sodiumbisulfite), e.g. primary paraffin sulfonates of about 1040, preferablyabout 15-20, carbon atoms; sulfates of higher alcohols; salts ofa-sulfofatty esters, (eg of about 10 to 20 carbon atoms, such as methylot-sulfomyristate or a-sulfotallowate).

Examples of sulfates of higher alcohols are sodium lauryl sulfate,sodium tallow alcohol sulfate. Turkey Red Oil or other sulfated oils, orsulfates of monoor diglycerides of fatty acids (e.g. stearicmonoglyceride monosulfate), alkyl poly (ethenoxy) ether sulfates such asthe sulfates of the condensation products of ethylene oxide and laurylalcohol (usually having 1 to 5 ethenoxy groups per molecule); lauryl orother higher alkyl glyceryl ether sulfonates; aromatic poly (ethenoxy)ether sulfates such as the sulfates of the condensation products ofethylene oxide and nonyl phenol (usually having 1 to 6 oxyethylenegroups per molecule).

The suitable anionic detergents include also the acyl sarcosinates (e.g.sodium lauroylsarcosinate) the acyl esters (e.g. oleic acid ester) ofisethionates, and the acyl N-methyl taurides (e.g. potassium N-methyllauroylor oleyl tauride).

The most highly preferred water soluble anionic detergent compounds arethe ammonium and substituted ammonium (such as mono-, diandtriethanolamine), alkali metal (such as sodium and potassium) andalkaline earth metal (such as calcium and magnesium) salts of the higheralkyl benzenesulfonates, olefin sulfonates, the higher alkyl sulfates,and the higher fatty acid monoglyceride sulfates. The particular saltwill be suitably selected depending upon the particular formulation andthe proportions therein.

Nonionic surface active agents include those surface active or detergentcompounds which contain an organic hydrophobic group and a hydrophilicgroup which is a reaction product of a solubilizing group such ascarboxylate, hydroxyl, amido or amino with ethylene oxide or with thepolyhydration product thereof, polyethylene glycol.

As examples of nonionic surface active agents which may be used theremay be noted the condensation products of alkyl phenols with ethyleneoxide, e.g., the reaction product of isooctyl phenol with about 6 to 30ethylene oxide units; condensation products of alkyl thiophenols with toethylene oxide units; condensation products of higher fatty alcoholssuch as tridecyl alcohol with ethylene oxide; ethylene oxide addends ofmonoesters of hexahydric alcohols and inner ethers thereof such assorbitan monolaurate, sorbitol mono-oleate and mannitan monopalmitate,and the condensation products of polypropylene glycol with ethyleneoxide.

Cationic surface active agents may also be employed. Such agents arethose surface active detergent compounds which contain an organichydrophobic group and a cationic solubilizing group. Typical cationicsolubilizing groups are amine and quaternary groups.

As examples of suitable synthetic cationic detergents there may be notedthe diamines such as those of the type RNHC H NH wherein R is an alkylgroup of about 12 to 22 carbon atoms, such as N-2-aminoethyl stearylamine and N-2-aminoethyl myristyl amine; amide-linked amines such asthose of the type R CONI-IC H NH wherein R is an alkyl group of about 9to carbon atoms, such as N-Z-amino ethylstearyl amide and N- amino ethylmyristyl amide; quaternary ammonium compounds wherein typically one ofthe groups linked to the nitrogen atom is an alkyl group of about 12 to18 carbon atoms and three of the groups linked to the nitrogen atom arealkyl groups which contain 1 to 3 carbon atoms, including such 1 to 3carbon alkyl groups bearing inert substituents, such as phenyl groups,and there is present an anion such as halogen, acetate, methosulfate,etc. Typical quarternary ammonium detergents are ethyl-dimethylstearylammonium chloride, benzyl-dimethyl-stearyl ammonium chloride,benzyl-dimethyl-stearyl ammonium chloride, trimethyl stearyl ammoniumchloride, trimethyl-cetyl ammonium bromide, dimethyl-ethyl dilaurylammonium chloride, dimethyl-propyl-myristyl ammonium chloride, and thecorresponding methosulfates and acetates.

Examples of suitable amphoteric detergents are those containing both ananionic and a cationic group and a hydrophobic organic group, which isadvantageously a higher aliphatic radical, e.g. of 1020 carbon atoms.Among these are the N-long chain alkyl aminocarboxylic acids, e.g. ofthe formula RN-R'COOM the N-long chain alkyl iminodicarboxylic acidse.g. of the formula RN(RCOOM) and the N-long chain alkyl betaines, e.g.of the formula where R is a long chain alkyl group, e.g. of about 10-20carbons, R is a divalent radical joining the amino and carboxyl portionsof an amino acid (e.g. an alkylene radical of 1-4 carbon atoms), M ishydrogen or a salt-forming metal, R is a hydrogen or another monovalentsubstituent (e.g. methyl or other lower alkyl), and R and R aremonovalent substituents joined to the nitrogen by carbon-to-nitrogenbonds (e.g. methyl or other lower alkyl substituents). Examples ofspecific amphoteric detergents are N-alkyl-beta-aminopropionic acid;N-alkylbeta-iminodipropionic acid, and N-alkyl, N,N-dirnethyl glycine;the alkyl group may be, for example, that derived from coco fattyalcohol, lauryl alcohol, myristyl alcohol (or a lauryl-myristylmixture), hydrogenated tallow alcohol, cetyl, stearyl, or blends of suchalcohols. The substituted aminopropionic and iminodipropionic acids areoften supplied in the sodium or other salt forms, which may likewise beused in the practice of this invention. Examples of other amphotericdetergents are the fatty imidazolines such as those made by reacting along chain fatty acid (e.g. of 10 to 20 carbon atoms) with diethylenetriamine and monohalocarboxylic acids having 2 to 6 carbon atoms, e.g.l-coco-S-hydroxethyl-5-carboxymethylimidazoline; betaines containing asulfonic group instead of the carboxylic group; betaines in which thelong chain substituent is joined to the carboxylic group without anintervening nitrogen atom, e.g. inner salts of Z-trimethylamino fattyacids such as 2-trimethyl aminolauric acid, and compounds of any of thepreviously mentioned types but in which the nitrogen atom is replaced byphosphorus.

The relative proportions of the hydroxyalkyl morpholine oxide and theother detergent may vary Widely, e.g. in the range of ratios of 100:1 to1:100; preferably about 5 to 30 parts of the morpholine oxide per 100parts of the other detergent are used.

A very suitable dishwashing liquid detergent may contain, for example, amixture of a linear higher alkylbenzene sulfonate and a higher alkylether sulfate in a ratio of about 0.411 to 1:1. In one type ofsulfate-alkylbenzenesulfonate highly eifective for this purpose, thealkylphenyl moiety has a molecular weight of 230 to 240; its alkyl groupis largely (at least mol percent) in the C10 to C12 range, at least halfof the alkyls in the C10-C12 range being C10 and C11, the C10 and C11being at least 45% of the total alkyl, at least 80% of the alkylsubstituent being alkyl groups having the benzene attachment on the 3-(or higher, e.g. 34-5- or 6-) carbon of the alkyl. The higher alkylether sulfate in this dishwashing formulation may, for example, have theformula R(OCH CH SO M where R is long chain alkyl of 10 to 15 carbonatoms, 11 is about 1 to 5 (e.g. about 3) and M is a cation such asammonium, sodium, potassium, mono-, dior triethanolammonium, etc.

Water-soluble builder salts may also be present, in the usualproportions, in the detergent formulations when heavy duty cleaning isdesired. These salts include phosphates and particularly condensedphosphates (e.g. pyrophosphates or tripolyphosphates), silicates,borates and carbonates (including bicarbonates), as well as organicbuilders such as salts of nitrilotriacetic acid or ethylene diaminetetracetic acid. Sodium and potassium salts are preferred. Specificexamples are sodium tripolyphosphate, potassium pyrophosphate, sodiumhexametaphosphate, sodium carbonate, sodium bicarbonate, sodiumscsquicarbonate, sodium tetraborate, sodium silicate, salts (e.g. Nasalt) of methylene diphosphonic acid, trisodium nitrilotriacetate, ormixtures of such builders, including mixtures of pentasodiumtripolyphosphate and trisodium nitrilotriacetate in a ratio, of thesetwo builders, of [:10 to 10:1, e.g. 1:1. The proportions of builder saltmay be, for example, 50 parts or more (e.g. 50 to 1000 parts) per partsof detergent. A granular heavy duty detergent composition for washingclothes may comprise, for example, about 1518% lineartridecylbenzenesulfonate of the type disclosed in Rubinfeld U .8. Pat.3,320,174, May 16, 1967, about 2050% hydrated pentasodiumtripolyphosphate, about 3 to 8% sodium silicate, about 25% of the N-2-hydroxydodecyl morpholine oxide, and the balance sodium sulfate. A heavyduty detergent liquid composition for washing clothes in cool water maycomprise, for example, an aqueous solution containing about 10% of anon-ionic detergent, about 25% of tetrapotassium pyrophosphate, about17% of the N-hydroxyalkyl morpholine oxide and about 4% sodium silicate.Optical brighteners and soil-suspending agents may be included in theusual minor amounts in each case.

In formulating the novel hydroxyalkyl morpholine oxides of thisinvention into skin lotions, the new compound may be incorporated intothe well known hand lotions containing water-immiscible materials suchas mineral oils, blends of liquid mineral oils with high boilingpetroleum fractions (such as paraffin wax, petrolatum or oxocerite),lanolin, fatty oil esters such as glyceryl monostearate, and fatty acidssuch as stearic or oleic acid. These water-immiscible materials may becomponents of an oil phase of an oil-in-water emulsion. A blend of about1-3 parts of mineral oil, about 0.5-2 parts of either lanolin or lanolinalcohol or a mixture of these, about 13 parts of fatty acid and about2-7 parts of polyhydroxy compound such as glyceryl monostearate may beused as the oil phase. The ratio of aqueous phase to oil phase istypically about :1 to 20:1. The aqueous phase may contain a detergentsurfactant, for example in concentration of about 0.1 to 5% of saidphase. The amount of the N-hydroxyalkyl morpholine oxide in the lotionmay be, for example, in the range of about 0.25%.

In a typical method for making the lotion comprising an oil-in-wateremulsion, the oil phase and water phase are heated (e.g. to 70-80 C.,say 74 C.) and the oil phase is added to the water phase and mixedthoroughly. The temperature is then lowered (e.g. to 35-50 C., say 40C.) and additional ingredients such as glycerine and calcium caseinateor other hydrophilic colloid are incorporated into the water phase ofthe emulsion.

The novel hydroxyalkyl morpholine oxides of this in- 'vention may beused in shampoo compositions in which they may be blended with anysuitable water-soluble anionic detergent, which may be one of the wellknown types used in shampoos, e.g. an alkyl sulfate of for example,12-18 carbon atoms, such as sodium lauryl sulfate or sodium tallowalcohol sulfate other sulfate detergents such as the triethanolammoniumsalt of the monosulfate of an ethoxylated lauryl alcohol (made from, forexample, 3 mols of ethylene oxide and one mol of coconut alcohol), or asulfonated detergent, such as an alkylbenzenesulfonate or olefinsulfonate or an amphoteric detergent such as an N-long chain alkylaminocarboxylic acid or an N-long chain alkyl iminodicarboxylic acid, aspreviously described herein. A typical shampoo composition may comprise,for example, an aqueous mixture containing about 1 to 15% of thehydroxyalkyl morpholine oxide and about to 30% of the other detergent,and may be in free flowing liquid, cream, or lotion form.

The novel hydroxyalkyl morpholine oxides of this invention may also beused as constituents of toilets bars, in admixture with conventionaltoilet soaps, such as the usual sodium soap of a mixture of about 3parts of tallow fatty acids and one part of coconut oil fatty acids, orin admixture with synthetic detergents such as the olefin sulfonatesmentioned above or the long chain fatty acid (e.g. coconut oil fattyacid) moonglyceryl sulfates. In one example, about parts of thehydroxyalkyl morpholine oxide is used with 100 parts of the otherdetergent (soap or synthetic).

The following examples are given to illustrate this invention further.In these examples, as in the remainder of the application, allproportions are by weight unless otherwise indicated.

EXAMPLE 1 20 grams of 1,2-epoxydodecane (B.P. 97-98 C. at 3.5 mm. Hg A)is heated with 9.7 grams of morpholine at 100 C. in a sealed containerfor 16 hours. The resulting mixture is then fractionally distilled andthe product is collected at a temperature of 119 C. and a pressure of0.05 mm. Hg A. 23.4 grams of N-2-hydroxydodecyl-morpholine having anequivalent weight of 273, by titration (as compared to the calculatedequivalent Weight of 271 for this compound) are obtained. This product(23.4 grains) is mixed with 9.74 grams of aqueous 30% hydrogen peroxideand 50 ml. of methanol and heated at 50 C. for 2 hours. Thereafter anyexcess peroxide is decomposed by adding 0.1 gram platinum black oncharcoal (of 5% Pt content) and heating the mixture at 40 C. for 4hours. The platinum-on-charcoal catalyst is filtered off, and thefiltrate is evaporated to recover the crude product, which is thenrecrystallized from 300 ml. of acetone to produce 17.5 grams of purifiedN-Z-hydroxydodecyl-morpholine N-oxide having a melting point of 151 2 C.(and having an equivalent weight by potentiometric titration inmethanol, equivalence point at pH 3.25, of 290; as compared to thecalculated equivalent weight of 287 for this compound).

EXAMPLE 2 A mixture of Cl-2-Cl6 alpha olefins is epoxidized inconventional manner to give a mixture of 1,2-epoxyalkanes of 1216 carbonatoms having an average molecular weight of about 207. 100 grams (0.48mol) of this epoxide mixture is heated with 46 grams (a 10% excess) ofmorpholine in a Parr bomb having a magnetically operated stirrer, andmaintained at a temperature of 100 C. overnight. The product is thendistilled at a subatmospheric pressure (1 mm. Hg A) and the fractionsdistilling at -185 C. (temperature of distilling head) are collected.The collected material is reacted with hydrogen peroxide as in Example1, to produce a white solid mixture of N-Z-hydroxyalkyl-morpholineoxides containing 12 to 16 carbons in the alkyl group.

EXAMPLE 3 Using the method described in Example 1, there is preparedN-Z-hydroxyoctadecyl-morpholine oxide of melting point 147148 C. Themeasured equivalent weight is 371.5 the equivalent weight calculated forthis compound is 371.6.

EXAMPLE 4 Tests of the foaming power of the compound of Example 1 aremade by shaking cylinders containing the following solutions:

'(a) a 0.05% solution of the compound in water;

(b) a solution of 0.05% of sodium linear alkylbenzenesulfonate detergentin water.

(c) a solution of 0.05% of the compound and 0.05% of the foregoingalkylbenzenesulfonate in water. It is found that solution (b) foams muchbetter than solution (a); and solution (0) yields more foam thansolution (b) and the foam is more stable.

EXAMPLE 5 The N-2-hydroxydodecyl-morpholine N-oxide is tested for itseffectiveness in reducing the skin irritation ordinarily caused byexposure to aqueous sodium lauryl sulfate. In this test there is used acontrol composition containing 2% of sodium lauryl sulfate in water, andan otherwise identical composition containing, in addition, 0.5% of thehydroxyalkylmorpholine oxide. Each composition is applied to the skin ofrabbits twice a day for two days, using six different skin sites foreach composition, and observing the irritation 48 hours after thebeginning of the test. The composition containing theN-2-hydroxydodecyl- 7 morpholine N-oxide is found to cause appreciablyless skin irritation.

EXAMPLE 6 A hand lotion is formulated from the following ingredicuts:

(a) an aqueous mixture of 74.4 parts deionized water, 1 part sodiumlauryl sulfate, 1 part of the hydroxyalkyl morpholine oxide of Example1, and, as preservatives, 0.18 part methyl p-hydroxybenzoate and 0.22part propyl p-hydroxybenzoate.

(b) a mixture of 2.0 parts light mineral oil, 5.0 parts glycerylmonostearate, 1.0 part lanolin alcohol (Amerchol H9) and 1.5 partstearic acid (triple pressed).

(c) a mixture of 3.0 parts glycerine, 0.5 part calcium caseinate and 5.0parts deionized water.

(d) a mixture of 1 part benzyl alcohol and 0.5 part perfume.

The oily mixture (b) is melted and added to the aqueous mixture (a)while the la tter is in heated agitated condition, to form an emulsion,which is allowed to cool. To the resulting warm mixture theglycerine-caseinatewater blend (c) is added, with stirring, and afterfurther cooling, to room temperature, the benzyl-alcohol-perfume mixture(d) is added. The presence of the 'benzylalcohol helps to control theviscosity of the lotion.

In tests of the protective effect of the lotion against irritation byprolonged contact with an irritating detergent solution (aqueous sodiumlauryl sulfate), the lotion of this example is found to give improvedprotection as compared to a similar hand lotion free of the hydroxyalkylmorpholine oxide.

EXAMPLE 7 A liquid detergent composition is formulated from thefollowing ingredients: sodium linear alkylbenzenesulfonate, 22%;ammonium salt of monosulfate of ethoxylated sulfated straight chainprimary alkanol (the alkanol having 1214 carbon atoms and theethoxylated product containing 3 ethylene oxide units per molecule),10%; mixed lauric/myristic (70/30) ethanolamide, 5%; N-2-hydroxydodecyl-morpholine oxide, 5%; ethanol, 5.3% sodium xylenesulfonate, 5.8%; and water, constituting substantially the remainder ofthe composition. A given amount of this detergent formulation is foundto be effective for washing a considerably greater number of greasedplates (36 vs. 27, in hard water) than an equal amount of an otherwiseidentical detergent formulation free of hydroxyalkyl morpholine oxide.

The alkylbenzenesulfonate is produced by sulfonation of an alkylbenzeneof molecular weight 238, containing mainly alkyl grgoups of to 12carbons.

EXAMPLE 8 Example 7 is repeated except that the fatty acidmonocthanolamide is omitted from the composition. The resultingdetergent composition is found to be effective for washing aconsiderably greater number of greased plates (33 plates) than otherwiseidentical formulations containing (a) the fatty acid monoethanolamide inplace of the hydroxyalkyl morpholine oxide (27 plates); (b) lauryldimethylamine oxide in place of the hydroxyalkyl morpholine oxideplates).

EXAMPLE 9 A liquid detergent composition is formulated from: thealkylbenzenesulfonate of Example 7, the ammonium alkyl ether sulfate ofExample 7, 4%; N-Z-hydroxydodecylmorpholine oxide, 5 ethanol, 5.1%;urea, 5 sodium xylene-sulfonate, 1.7%. The resulting formulation isfound to be effective for washing a considerably greater number ofgreased plates (39, in hard water) than an otherwise identicalformulation containing lauryl dimethylamine oxide in place of thehydroxyalkyl morpholine oxide (30 plates).

8 EXAMPLE 10 In another variation of the method of preparation of thenovel compounds, one mol of the 1,2-epoxyalkane (e.g. 1,2-epoxydodecane)is reacted with 1.5 mols of morpholine under reflux at atmosphericpressure for 4 hours until all the epoxide has reacted. The excess ofmorpholine is then distilled off under vacuum, the reaction product iscooled to 50 C., and 1.05 mols of aqueous 35% hydrogen peroxide areadded slowly While the mixture is stirred and cooled to maintain itstemperature below C. Toward the end of the reaction the mixture isdiluted with water so that it can still be stirred readily. The mixtureis then heated to 8590 C. for one hour. When 1,2-epoxy dodecanc is usedas the starting material, there is obtained a slightly yellow solutionwhich slowly solidifies to a paste and which contains 59.5%N-2-hydroxydodecyl-morpholine oxide and 1.2%N-2-hydroxydodecyl-morpholine in water.

tEXAM PLE 1 1 Following the procedure of Example 10, the following2-hydroxyalkyl morpholine oxides are prepared from the corresponding1,2-epoxyalkane (e.g. using 1,2-epoxy nonane for making thehydroxynonyl-morpholine oxide). After crystallization as in Example 1,the product has the indicated melting point.

M.P., C N-2-hydroxynonyl-morpholine oxide 149-150N-Z-hydroxyundecyl-morpholine oxide 150.5151.5

N-2-hydroxytridecyl-morpholine oxide 151-152N-2-hydroxytetradecyl-morpholine oxide 2. 151-152N-2-hydroxypentadecyl-morpholine oxide 151-152 N-2-hydroxyhexadecyl-morpholine oxide 15 1-1 5 2N-2-hydroxyheptadecyl-morpholine oxide 15 041 51 EXAMPLE 12 Anotherliquid detergent composition contains 23% of the sodium linearalkylbenzenesulfonate of Example 7, 13% of the ammonium salt of sulfatedethoxylated alkanol of Example 7, 5% of the N-2-hydroxydodecylmorpholine oxide (supplied as the paste of Example 10), 5% of sodiumxylene-sulfonate (hydrotrope). The mixture is adjusted to a pH of 7.5.In a test of its dishwashing performance, it is found to washconsiderably more plates (in water of 150 ppm. hardness) before the foamdisappears than an otherwise identical formulation containing 5%lauric/myristic monoethanolamide or 5% lauric/ myristic diethanolamidein place of the material of Example 10. The clear point of the productis 32 F. in contrast to clear points of 44 F. and 52 F., respectively,of the two liquid formulations used for the comparisons.

EXAMPLE 13 0.25 g. of N-2-hydroxydodecyl-morpholine oxide is added to 25cc. of distilled water at room temperature (25 C.) with continuousstirring. The material dissolves quickly. The temperature of thesolution is raised slowly to C. and then cooled in an ice bath. Thesolution is found to be clear; the dissolved material does not come outof solution until the temperature is reduced to 2 C. In contrast, inthis test, N-2-hydroxydodecyl-diethanolamine oxide forms a cloudymixture at the outset.

EXAMPLE 14 This example illustrates a liquid detergent for use in themachine-washing of clothes in cool water.

A liquid detergent is prepared by mixing in the following order, at atemperature of -180 F., 32.3 parts of water; 0.005 part of a non-ionicdetergent which is a polyoxyethylated nonyl phenol (specifically acondensation product of 15 mols of ethylene oxide and 1 mol of nonylphenol); and 1 part of a copolymer of vinylmethyl ether and maleicanhydride (Gantrez AN-908); under these conditions the anhydride ring ofthe copolymer opens, forming an acidic partial ester with thepolyethoxylated nonyl phenol. There are then added 1.6 parts of anaqueous 45.4% solution of KOH; 0.69 part of sodiumcarboxymethylcellulose; 2 parts of a 10% aqueous dispersion offluorescent brighteners; 1.7 parts of an aqueous 1% solution of blue dye(Polar Brilliant Blue); 0.12 part of an aqueous 0.5% solution of greendye (D & C Green #8); 8.56 parts of aqueous sodium silicate of 43.5%concentration in Which the Na O:SiO mol ratio is 1:235); 10 parts of anon-ionic detergent which is a polyoxyethylated alkyl phenol(specifically a condensation product of 10 mols of ethylene oxide andone mol of branched chain dodecyl phenol); 1 to parts ofN-hydroxydodecylmorpholine oxide; and 41 parts of an aqueous 60%solution of tetrapotassium pyrophosphate, together with a small amountof perfume. The brighteners used in the above formulation include (a)0.08 part of Geigy Tinopal RBS-200%, a naphthotriazole stilbenesulfonate brightener, and (b) 0.12 part of another stilbene brightenerbis (anilino diethanolamino s-triazinyl) stilbene disulfonic acid.

EXAMPLE 15 (a) A shampoo composition is prepared by mixing 2 to 5%N-2-hydroxydodecyl-morpholine oxide, triethanolammonium lauryl sulfateand, the balance, water.

(b) In another shampoo composition there is used 10% of sodiummonosulfate of ethoxylated lauryl alcohol (made with 3 to 4 mols ofethylene oxide per mol of lauryl alcohol) in place of thetriethanolammonium lauryl sulfate.

(c) Another shampoo composition contains 10% of triethanolamine oleate,9% of N-Z-hydroxydodecylmorpholine oxide, and 1.6% of a cationicdispersing agent, oleyl dimethyl benzyl ammonium chloride and, thebalance, water.

(d) A shampoo composition, in gel form, contains 68% of an aqueous 41%solution of triethanolammonium lauryl sulfate; 6% sorbitol; 4% ethylalcohol; 1.8% methyl cellulose, serving as a thickener; 5%lauric-myristic diethanolamide; 1% N 2 hydroxydodecyl-morpholine oxide;a small amount of formaldehyde as a preservative and the balance water.The pH is adjusted to 7.2; as by addition of triethanolamine.

While the invention finds its greatest utility in the embodiment inwhich the unsubstituted Z-hydroxyalkyl morpholine oxides are used, it isalso within the broader scope of this invention to use long chain3-hydroxyalkyl morpholine oxides (which may be made in the same way asthe corresponding 2-hydroxyalkyl compounds, using the corresponding 1,3oxetane in place of the 1,2 epoxide) and to use compounds in which thereis a substituent such as lower alkyl (e.g. methyl, ethyl or propyl) onone or more of the carbon atoms of the morpholine ring, form ing suchcompounds as N-(3-hydroxydodecyl) morpholine oxide orN-(Z-hydroxyhexadecyl) Z-methylmorpholine oxide.

It is to be understood that the foregoing detailed description is merelygiven by Way of illustration and that many variations may be madetherein without departing from the spirit of the invention. The Abstractgiven above is merely for the convenience of searchers and is not to begiven any weight in defining the scope of the invention.

What is claimed is:

1. A morpholine oxide of the formula where R is alkyl of six to twentycarbon atoms.

2. A morpholine oxide as in claim 1 in which R has 6 to 20 carbon atoms.

References Cited UNITED STATES PATENTS 3,413,292 11/19-68 Johnson, Jr.260247.7

ALEX MAZEL, Primary Examiner J. TOVAR, Assistant Examiner U.S. Cl. X.R.

